Azo-azoxy dyes



I soap-soda and to Patented Apr. 5, 1949 AZO-AZOXY DYES Ernst Keller,

Basel, Switzerland, assignor to .L-lt.

Geigy A. G.,.Basel, Switzerland, a Swiss firm No Drawing.- ApplicationMay 14, 1945,

Serial No.'593,771 In Switzerland June 27, 1944 Claims. (Cl. 260-143) 1'I have found'that valuable azo dyestuils are obtained by condensingnitromonoazo dyestuffs oi the general formula 4 R.N=N.R1NO2 I wherein Rmeans an aryl radical withan o-hy droxy carboxylic acid a p-phenyleneradical, which may be further substituted, in an alkaline medium withaminodiphenylamine derivatives containing at least one.

such as a sulfonic acid or carboxyl group. The condensation can alsobewater-solubilising group,

carried out under pressure. The interaction probably takes place in amanner similar to that resulting when condensing dinitrostilbene disul-,

ionic acids or derivatives of nitroaminostilbene disulfonic acid withamines, that is to say by forming particularly azoxy azo dyestuffs.

The new dyestufis which are obtainable according to the above method maybe used for the dye- .ing of wool according to the after-chroming methodor for the dyeing of leather. The same :are especially suitable forchrome-printing onto lcellulosic fibres. Thus especially reddish-brownto deep brown prints are obtained which are distinguished by'goodfastness properties to soaps, light and which are particularly fast tochlorine. The dyestuffs are dark-brown powders which dissolve inwaterflwith an orangebrown to red-brown coloration. e

The invention will be illustrated by the follow- :ing examples, withoutbeing limited thereto; the 'parts are by weight.

Example 1 36.7 parts of4-nitro-4'-hydroxy-1:lazobenzene-3'-carboxy-2-sulfonic acid and 26.4parts of 4-aminodiphenylamine-2-sulfonic acid are heated for 12-16 hoursto boiling underreflux with 600 parts of 8% caustic soda lye. Thenfurther 600 parts of water are added and at 80-90 0., small quantitiesof a diflicultly soluble by-product thus produced are filtered off. Now,the alkalinity of the filtrate is decreased by means of hydrochloricacid until a slightly alkaline reaction has been reached, whereupon thecondensation product is completely precipitated by means of sodiumchloride and dried.

. The dyestufl produces, onv chrome-printing, full reddish-brown shadesonto cellulosic fibres,

grouping and R1 represents the dyeings thus obtained being very fast tosoapsoda, chlorine and to light. 1

A dyestufl having practically the same properties isobtained bycondensing, instead of under reflux, for 6-8 hours in -115 C.

. Example 2 35 parts of 4-nitro-4'-hydroxy'-1:1-azobenzene-3-carboxy-2-sulfonic acid and 32.4 parts of 4-amino 4'hydroxydiphenylamine 3' carboxylic-acid-Z-sulfonic acid are heated toboilin under reflux and for 12-16 hours in a stirred vessel with 600parts of 4% caustic soda lye. After the pressure-vessel at dilution with800 parts of water the difiicultly soluble lay-product is filtered oiland the dyes-tuft isolated as described in ExampleL v On chrome-printingonto cellulosic fibres deep reddish-brown shades of good fastness toboiling, to soap, soap-soda, to chlorine as well as to light areobtained.

Example 3 36.7 parts of4'-nitro-4'-hydroxy-1:1'--azobenzone-3'-carboxy-2-sulfonic acid and 40.4parts of 4-amino 4 hydroxydiphenylamine 3' --car iboxy-2z5-disulfonicacid are condensed at boiling temperature for 12-14 hours under refluxwith 600 parts of 8% caustic soda lye. After separation of smallquantities of a difficultly soluble byproduct, the dyestuff is isolated.

The dyestuff yields, on chrome-printing onto cellulosic fibres, veryfull reddish-brown shades of good fastn'ess properties in the moiststate and of good fastness to chlorine and-to light.

Another dyestufi having almost the same fastness properties is obtainedby replacing the4- nitro-4'-hydroxy 1:1 azobenzene 3' car boxy-2-suliomcacid by 4-nitro-2-methyl-4'-' hydroxy-1:1'-azobenzene 3 carboxy 2sulfonic acid.

Example 4 31.7 parts of 4-nitro-2-methoxy-4'-hydroxy-'1:1'-azobenZene-3-carboxylic acidand 34.4 parts of4-aminodiphenylamine-2:3'- 'disulfonic :acid are boiled under reflux for12-14 hours with 1000 parts of 5% caustic soda lye and, after havingclarified the solution, worked up in the usual manner.

The new dyestufi yields, on chrome-printing onto cellulosic fibres,reddish-brown shades of good fastness properties in the moist state andof good light-fastness.

Example 5 28.7 parts of 4-nitro-4-hydroxy-l:1'-azobenzene-3'-carboxylicacid and 26.4 parts of 4- aminodiphenylamine-2-sulfonic acid arecondensed at boiling temperature for 12-14 hours under reflux with 600parts of 8% caustic soda lye. After separation of the difficultlysoluble by-product the new dyestufi is isolated in the usual manner.

The resulting dyestufi dyes chrome-leather in full, orange-brown shades;on chrome-printing, reddish-brown shades of good fastness properties inthe moist state and of good light-fastness are produced onto cellulosiefibres.

The following table contains a certain number of further dyestuffsobtainable according to this invention:

nitromonoazo dyestufi medium 4-nitro-4-'hydroxy-1:1'-azobenzene-3'-diphenylamine derivative" carboxylic acid with 4-aminodiphenylamine-2-sulfonic acid.

' 6. The azo formula dyestufis of the probable general shade of thecondensation product obtained with the chrome printing method4-nitro-4'-hydroxy-l:1'-azobenzcne-3-carboxylic acg -sulionic acid.

ionic acid 4-nitro-2-methyl-4'-hydroxy-l:l-azo-benzene-5- 4-amlno 4'hydroxydiphenylamine- 3'- carboxylic scid-2:5'-disulfonic acid. i-amino-4'-hydroxydi phenylamme- 3'- carbox cagioxylic acid-2-sulfonic acid.

4-an%no-4'- methoxy diphenylsmine-iisulfonic sci a-an idnd2': 4'-dimethyldiphenylemine-2-sulfonic aci 4-aminodiphenylamine-3-carbcxylicacid-2-sulreddish-brown.

i-nitro-5-methy1-4'-hydroxy-2-methoxy-1:1'-azobegzene-If-carboxylicacid. l

4-nitro-2:5-dimethoxy-4 hydroxy- 1:l'-azobenzene-3'-carboxylic acid.

ylie acid-2-sulfonic acid. i-aminodiphenylamine-Z-sulionic acid 4-amino-4- hydxoxydi phenylamine 3" carboxylic acid-Zsulfonic acid.

-amine- 4% hydroxydi phenylamine 3- carboxylic acid-2:5'-disulfonicacid.

4-aminodiphenylamine-2suliomc acid i-aminodiphenylaminefifi disulfonicacid Q-amino -4'- hydroxydiphenylamine 3'- earb oxylicacid-2:5'-disulfonic acid.

What I claim is: 1. A process for the manu wherein It means an aromaticradical of the benzene series containing a OH and a COOH group ino-position to one another and R1- means a p-phenylene radical, with anaminodiphenylthe general formula amine derivative of wherein'X means amember select group consisting of H. OH, OCHs, and 5031-1.

2. A processstuffs, comprising condensing in medium anitro-monoazoformula I COOH wherein R1 means a p-phenylene radical, withderivative of the general an aminodiphenylamine formula SOQI X acture ofazo dyestuffs, comprising condensing in an alkaline medium anitro-monoazo dyestuff of the general ed from the for the manufacture ofazo dyedyestufi of the general QNHQ.

wherein R. means an aromatic benzene series containinga OH CH3, COOH andSOsH, being dark dissolving in water with coloration and dyeingcellulosic brown shades.

radical of the and a COOH group in o-position to one another, R1 means ap-phenylene radical and X means a member selected from the groupconsisting of H, 0-H, OCHs,

brown powders,

a brown to red-brown fibres in the chrome-printing process red-brown todark 7. The azo dyestuffsof the probable general formula CH3, COOH analkaline c5 sisting of H, OH, OCHs,

wherein R1 means a p-phenylene radical and X means a member selectedfrom the group con- CH3, COOH and SOaI-I, being dark brown powders,dissolving in water with a brown to red-brown coloration and dyeingcellulosic fibres in the chrome-printing process ,70 8. The azo dyestufiof being a.

red-brown to dark brown shades.

the probable-formula no -N=N N=N NH OOH 0,11 0 0,11

dark brown powder, dissolving in water i with a brown-orange colorationand dyeing cellulosic fibres in the chrome-printing processreddish-brown shades.

9. The azo dyestuft' of the probable formula H0 N=N N=N NH 011 P Q" Q Q0011 S0311 0 son;

0003 being a dark brown powder, dissolving in water with a brown-orangecoloration and dyeing cellulosic fibres in the chrome-printing processreddish-brown shades.

10. The azo dyestufi of the probable formula being a dark brown powder,dissolving in water with a brown-orange coloration and dyeing cellulosiofibres in the chrome-printing process reddish-brown shades.

ERNST KELLER.

6 REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS

